Modified molecular sieves by means of solid ion exchange

ABSTRACT

Molecular sieves are modified by an ion exchange process where metal cations are introduced into the molecular sieves by means of solid state ion exchange. The solid state ion exchange can be carried out as follows: a weighed amount of calcined and activated zeolite is intimately mixed with a precalculated amount of PtCl 2 , PdCl 2 , RhCl 3 , CuCl 2 , V 2  O 5  or another compound of the noble metals (e.g., corresponding halides or oxides), the solids mixture is then heated in a current of inert gas (e.g., a current of helium gas or of nitrogen) to temperatures of 400° to 600° C., then cooled down to room temperature and subsequently reduced in a current of hydrogen for 10 to 14 hours at 280° to 350° C. in order to produce small metal clusters from the cationically introduced metal.

This is a divisional of application Ser. No. 08/197,481, filed on Feb.16, 1994, now U.S. Pat. No. 5,434,114.

INTRODUCTION AND BACKGROUND

The present invention relates to a method of modifying molecular sievesby means of solid state ion exchange and the modified molecular sievesproduced thereby. In a more detailed aspect, the present inventionrelates to hydrogenation catalysts selective as to the form of productproduced and a method for hydrogenating olefinic compounds to formalkanes using said catalysts.

A known method for introducing noble metals such as platinum orpalladium into medium-pored and wide-pored zeolites is by way of ionexchange in aqueous suspension with the appropriate tetraamine complexes(e.g., Pt(NH₃)₄ Cl₂ or Pd(NH₃)₄ Cl₂). This method yields a highdistribution of the noble metal in the crystallite interior ofwide-pored zeolites (e.g., Y) and medium-pored zeolites (e.g., ZSM-5).

However, small-pored zeolites (e.g., ZSM-58, zeolite A) can not be dopedin this manner with platinum or palladium because the noble-metalcomplex is too bulky to be able to diffuse into the eight-metered ringchannels of these zeolites. The only known method for introducing noblemetals into the interstices of small-pored zeolites is to add thenoble-metal complex in the desired amount to the synthesis gel for thezeolite production prior to crystallization so that the zeolitecrystallizes around the complex (P. B. Weisz and V. J. Frilette, J.Phys. Chem. (1960), volume 64, page 382; P. B. Weisz et al., J. Catal.(1962), volume 1, pages 307-312). A shape-selective hydrogenationcatalyst can be produced in a known manner by introducing for examplePt(NH₃)₄ Cl₂ into the synthesis gel for zeolite A.

The known method for doping small-pored zeolites has the disadvantagethat it is not universally applicable to all zeolite types. The presenceof slight amounts of impurity, as in this instance the noble-metalcomplex, in the synthesis gel hinders the crystallization of the desiredzeolite.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a method for modifyingmolecular sieves which is characterized in that cations are introducedinto the molecular sieves by means of solid state ion exchange.Zeolites, especially small-pored zeolites, can be used as the molecularsieves in accordance with the invention. Cations of a metal from thefirst to the eighth subgroups of the Periodic Table can be used ascations; in particular, cations of the elements platinum, palladium,molybdenum and/or vanadium can be used. Another object of the presentinvention is to provide the modified molecular sieves produced by such amethod.

Still a further object of the present invention is to provide shapeselective hydrogenation catalysts and a method for hydrogenatingolefinic compounds to form alkanes using said catalysts.

The above and other objects of the present invention can be achieved bya process of solid state ion exchange that can be carried out asfollows: a weighed amount of calcined and activated zeolite isintimately mixed with a precalculated amount of PtCl₂, PdCl₂, RhCl₃,CuCl₂, V₂ O₅ or another compound of the noble metals (e.g.,corresponding halides or oxides) containing the noble metal, theresulting solids mixture is then heated in a current of inert gas (e.g.,a current of helium gas or of nitrogen) to temperatures of 400° to 600°C., then cooled down to room temperature and subsequently reduced in acurrent of hydrogen for 10 to 14 hours at 280° to 350° C. in order toproduce small metal cations clusters from the introduced metal. The flowrate of hydrogen can vary, but typically is about 15 cm³ /min.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be further understood from a study of thedrawings, wherein:

FIG. 1 is a graph which shows yields of n-hexane and2,4,4-trimethylpentane in the conversion of thehexene-(1)/2,4,4-trimethylpentene-(1) mixture on 1.0 Pt/ZSM-58 withn_(Si) /n_(Al) =50;

FIG. 2 is a graph which shows yields of n-hexane and2,2,4-trimethylpentane in the conversion of thehexene-(1)/2,4,4-trimethylpentene-(1) mixture on 0.54 Pd/ZSM-58 withn_(Si) /n_(Al) =50;

FIG. 3 is a graph which shows yields of n-hexane and2,2,4-trimethylpentane in the conversion of thehexene-(1)/2,4,4-trimethylpentene-(1) mixture on 1.0 Pt/RhO;

FIG. 4 is a graph which shows yields of n-hexane and2,2,4-trimethylpentane in the conversion of thehexene-(1)/2,4,4-trimethylpentene-(1) mixture on 0.9 Rh/ZK-5;

FIG. 5 is a graph which shows yields of n-hexane and2,2,4-trimethylpentane in the conversion of thehexene-(1)/2,4,4-trimethylpentene-(1) mixture on 1.0 Pd/Alpha;

FIG. 6 is a graph which shows yields of n-hexane and2,2,4-trimethylpentane in the conversion of thehexene-(1)/2,4,4-trimethylpentene-(1) mixture on 1.0 Pd/SAPO-42;

FIG. 7 is a graph which shows yields of hydrogenation products in thehydrogenation of the hexene-(1)/2,4,4-trimethylpentene-(1) mixture on1.0 Ni/SAPO-42 (produced by solid state ion exchange of SAPO-42 withNiCl₂); and

FIG. 8 is a graph which shows yields of hydrogenation products in thehydrogenation of the hexene-(1)/2,4,4-trimethylpentene-(1) mixture on1.0 Ni/SAPO-42 (produced by solid state ion exchange of SAPO-42 withNiO).

DETAILED DESCRIPTION OF THE INVENTION

The principle of solid ion exchange is known as is shown in H. G. Kargeand H. K. Beyer in "Zeolite Chemistry and Catalysis", P. A. Jacobs etal., editor, pp. 43-64, Studies in Surface Science and Catalysis, vol.69, Elsevier, Amsterdam, Oxford, New York, Tokyo (1991), which arerelied on and incorporated by reference in their entirety.

The method of the present invention can be used with advantage with thefollowing small-pored molecular sieves or zeolite types:

Zeolite ZSM-58 (described in EP 193,282), molecular sieves with thestructure of zeolite A (e.g., zeolite Alpha described in U.S. Pat. No.3,375,205) or SAPO-42 (described in U.S. Pat. No. 4,440,871), zeoliteRho (described, among other places, in J. Catal. (1988), volume 113,pages 367-382), and zeolite ZK-5 (described in U.S. Pat. No. 3,720,753).U.S. Pat. Nos. 3,375,205; 3,720,753; and 4,440,871 are incorporated byreference in their entirety. In general, the term "fine-pored" or"small-pored" zeolite is a material the pores of which are formed byeight-membered oxygen rings (viz., rings made up of eight TO₄-tetrahedra).

In order to be able to distinguish qualitatively between metal clusterswithin the pore system versus metal clusters on the outer crystallitesurface of the zeolite, the well known educt-selective catalytichydrogenation introduced by Dessau (R. M. Dessau, J. Catal. (1982),volume 77, pages 304-306), for example, can be used wherein a mixture ofthe same amounts of substance of a straight chain and of a bulky alkene(e.g., hexene-(1) or pentene-(1) and 2,4,4-trimethylpentene-(1)) isused.

The method for modifying molecular sieves by means of solid state ionexchange is characterized in that cations are introduced into themolecular sieves by means of solid state ion exchange. Such a process ofsolid state ion exchange can be carried out as follows: a weighed amountof calcined and activated zeolite is intimately mixed with aprecalculated amount of PtCl₂, PdCl₂, RhCl₃, CuCl₂, V₂ O₅ or anothercompound of the noble metals (e.g., corresponding halides or oxides)containing the noble metal, the resulting solids mixture is then heatedin a current of inert gas (e.g., a current of helium gas or of nitrogen)to temperatures of 400° to 600° C., then cooled down to room temperatureand subsequently reduced in a current of hydrogen for 10 to 14 hours at280° to 350° C. in order to produce small metal clusters from theintroduced metal cations. The flow rate of hydrogen can vary, buttypically is about 15 cm³ /min.

Concerning the precalculated amount of PtCl₂, PdCl₂, RhCl₃, CuCl₂, V₂ O₅or another compound of the noble metals (e.g., corresponding halides oroxides) containing the noble metal, it is assumed that virtually all ofthe metal offered during the step of solid state ion exchange isexchanged into the zeolite; thus, the amount of the metal salt to beused for reaching the desired metal loading can be calculated on thebasis of simple chemical stoichiometry.

Calcined and activated zeolites used herein as starting materials arewell known to those skilled in the art. In general, calcination involvestreatment of the zeolite at elevated temperatures (e.g., 400° to 600°C.) in an oxygen containing atmosphere to burn off organic materials(e.g., templates) occluded in the voids of the zeolite. In general,activation involves rendering the zeolite active for adsorptive orcatalytic applications (e.g., desorption of water at elevatedtemperatures; decomposition of NH₄ ⁺ ions in a zeolite at elevatedtemperatures to yield the Bransted acid H⁺ form). In many instances,calcination and activation are separate steps. However, if there are noalkali cations present in the zeolite, calcination and activation (viz.,decomposition of the template and formation of acid sites) may occursimultaneously (i.e., the organic template is burnt off and leavesbehind a proton).

If the metal introduced via solid state ion exchange is an oxidationcatalyst (e.g., a metal known to be active as an oxidation catalyst, forexample Cu, Co, Pt, Pd, Ru, Rh, Fe and others), the test reaction can becarried out for example with a gaseous mixture consisting of an n-alkaneand a strongly branched isoalkane with air or oxygen as carrier gas.

The exchanged molecular sieves or zeolites (e.g., hydrogenationcatalyst) produced in accordance with the method of the presentinvention are distinguished in that in the test reaction theyhydrogenate the alkene and oxidize the n-alkane with high selectivity.Surprisingly, as a result of the method of the present invention, thepredominant part (>60%, preferably >70%) of the introduced metal islocated in the pores and interstices of the small-pored zeolites; onlythese molecular sieves are suitable as catalyst for form-selective,metal-catalyzed reactions. By comparison, small-pored zeolites producedin a known manner (i.e., charged with metal by means of ion exchange inaqueous suspension) are not form-selective; the metal is located on theouter surface of the zeolite crystallites and is therefore also freelyaccessible for bulky molecules.

The modified molecular sieve produced by the method of the presentinvention may be a hydrogenation catalyst. Such hydrogenation catalystsmay be utilized in a method for hydrogenating olefinic compounds to formalkanes involving hydrogenating olefinic compounds with thehydrogenation catalyst. The size of the individual zeolite crystallitesis usually 0.5 to 5 μm. For the catalytic experiments, the crystallitesare pressed without any binder, crushed and sieved to a size fractionbetween 0.3 and 0.5 mm. However, it is expected that similar results canbe obtained if the catalysts are agglomerated using a binder ordifferent shapes of the pellets. The useful pore size depends on thesize of the feed olefin. In the examples, most zeolites are those havingsmall pores (eight-membered rings) or medium pores (ten-membered rings)zeolites. For the conversion of bulkier molecules, even large pore(twelve-membered rings) zeolites may be useful.

EXAMPLES EXAMPLE 1

It is advantageous to first prepare the Bransted acid (H⁺ -) form of thezeolite and to subject this to solid state ion exchange in accordancewith the present invention; in this way, the metal cation is introducedinto the zeolite and HCl is produced, no residual cations remain in thezeolite.

Zeolite ZSM-58 with a modulus of (n SiO₂ /n Al₂ O₃)=50 is synthesizedaccording to EP 193,282 with methyltropinium iodide as template,subsequently calcined 16 hours at 540° C. in air, and then subjected toa multiple ion exchange in aqueous suspension with a large excess of NH₄NO₃ solution. The Bransted acid (H⁺ -) form is obtained by thesubsequent calcination at 550° C.; from it, approximately 0.5 g (drymass) at a time is treated for 12 hours at 550° C. in a current ofhelium (V_(He) =33 cm³ /min.). Then the zeolite activated in this manneris intimately mixed at room temperature under inert gas with 0.007 gPtCl₂ or 0.009 g PdCl₂ to carry out the solid state ion exchange. Themixture is heated in a dry current of helium (VHe=33 cm³ /min.) at arate of 3 K/min. to 550° C. (with PtCl₂) and 480° C. (with PdCl₂). Twomoles HCl gas are produced per mole PtCl₂ and PdCl₂ exchanged during thesolid state ion exchange. The development of HCl is followeddifferentially with a thermal-conductivity detector or a massspectrometer and integrally by absorption of the hydrogen chloride indemineralized water via the increase of the electric conductivity of theabsorption liquid; such methods are well known in the art. Aftertermination of the solid state ion exchange the hydrochloric acidproduced is titrated with 0.01 m NaOH solution and bromothymol blue asindicator. The results are presented in table 1:

                  TABLE 1                                                         ______________________________________                                                 n MeCl.sub.2,                                                                             n Cl.sup.-,                                                                              m Me/m Z                                      MeCl.sub.2                                                                             in, mol     out, mol   %                                             ______________________________________                                        PtCl.sub.2                                                                             2.6 × 10.sup.-5                                                                     5.1 × 10.sup.-5                                                                    1.0                                           PdCl.sub.2                                                                             5.1 × 10.sup.-5                                                                     1.1 × 10.sup.-4                                                                    1.2                                           MeCl.sub.2 :                                                                           metal (Me) salt used                                                 n MeCl.sub.2, in:                                                                      weighed-in amount of MeCl.sub.2 substance                            n Cl.sup.-, out:                                                                       titrated amount of chloride ion substance                            m .sub.Me /m.sub.z :                                                                   charge of the dry zeolite with metal after                                    the solid ion exchange                                               ______________________________________                                    

It is apparent from the data in table 1 that the solid state ionexchange occurs practically totally at the amount ratios used here andunder the conditions employed. The exchanged zeolites contain 1.0% byweight PtCl₂ or 1.2% by weight PdCl₂.

EXAMPLE 2

Bransted acid centers arise in the reduction of the metal cations withhydrogen introduced by solid ion exchange into the zeolites; suchcenters can catalyze undesired side reactions under reaction conditions(e.g., isomerization or cracking). In order to avoid this, all catalystsare rinsed before the start of the tests for 15 minutes at reactiontemperature with pure ammonia, which poisons the acidic centers;otherwise, Bransted acid sites may catalyze undesired side reactions(e.g., double bond isomerization or skeletal isomerization).

Zeolite HZSM-58 is exchanged in accordance with the method described inexample 1 via solid state ion exchange with platinum or palladium. Thenoble-metal contents are 1.0% by weight Pt and 0.54% by weight Pd. Theexchanged zeolites are reduced at 300° C. in a current of hydrogen. Theacidic centers produced thereby are poisoned by rinsing with ammonia at110° C. and tested in the hydrogenation of thehexene-(1)/2,4,4-trimethylpentene-(1) mixture under the followingtypical conditions:

Reaction temperature: T=50° to 110° C.

Modified dwell time: W/F_(olefines) ≈3 to 30 g•h/mole

Partial hydrogen pressure: P_(H) ≈100 kPa,

Partial pressure of the alkenes: P_(olefines) ≈7 to 14 kPa

Catalytic mass (dry): W=0.50 g

The results of the catalytic tests are shown in FIGS. 1 and 2. Theyields of the hydrogenation products n-hexane and 2,4,4-trimethylpentaneare plotted as a function of the time. It is apparent that thehydrogenation of hexene-1 is strongly preferred on both catalysts. Theintroduction of platinum and palladium via solid state ion exchange intosmall-pored zeolite ZSM-58 and the production therewith of aform-selective hydrogenation catalyst was therefore successful.

Conventional equipment used for hydrogenation can be used for purposesof the present invention. The olefin is contacted with the hydrogenationcatalyst of the invention in the customary fashion known in the art.

EXAMPLE 3 REFERENCE EXAMPLE

Zeolite HZSM-58 is replaced via ion exchange in aqueous solution ofPt(NH₃)₄ Cl₂ and Pd(NH₃)₄ Cl₂ with 2% by weight platinum and 1.1% byweight palladium (corresponding to the same substance amounts of Pt andPd). For the ion exchange in aqueous solution, approximately 5 g zeoliteare suspended in 200 cm³ water in each instance. To this endapproximately 100 cm³ water are added drop by drop over a period of 3hours under constant agitation in which water a precalculated amount ofthe noble-metal complex is dissolved. The suspension is subsequentlyagitated for a further 24 hours and then evaporated to low bulk in arotary evaporator until dry. The powder obtained in this manner is driedovernight at 120° C. in a drying oven.

It is necessary in the method described here for introducing noble metalvia ion exchange with aqueous solutions of the tetraammine complexes tofirst break down the exchanged noble-metal complex by an O₂ treatmentbefore the reduction in the current of H₂ if a good dispersion of thenoble-metal complex is to be assured (cf. P. Gallezot, Catal. Rev.-Sci.Eng. (1979), volume 20, pages 121-154). The exchanged zeolite is treatedfor 16 h at 300° C. in a current of oxygen (VO₂ =16 l/h) and then for 16h at 300° C. in a current of hydrogen (V_(H) =6 l/h). The exchangedzeolites are subsequently tested in the catalytic hydrogenation of themixture of the same amounts of substance of hexene-(1) and2,4,4-trimethylpentene-(1) as described in example 2. Both olefines are100% hydrogenated on both catalysts under the conditions describedabove. It is therefore not possible to produce a form-selectivehydrogenation catalyst by means of ion exchange in aqueous solution.

EXAMPLES 4 TO 9

Zeolite Rho is synthesized as described in J. Catal. (1988), volume 113,pages 367-382. Zeolite ZK-5 is synthesized according to U.S. Pat. No.3,720,753 and zeolite Alpha according to U.S. Pat. No. 3,375,205. Thesynthesis of SAPO-42 takes place according to U.S. Pat. No. 4,440,871.These zeolites are, as described in example 1, calcined, converted bymeans of ion exchange in aqueous solution into the ammonium form and bymeans of subsequent calcination into the H⁺ form and subsequently usedin the solid state ion exchange. The amounts and the type of metal saltused, the amount of recovered chlorine substance as well as the metalcharging of the zeolite achieved after the reduction in a current ofhydrogen, which takes place in the manner described in example 1, arecollected in table 2.

                                      TABLE 2                                     __________________________________________________________________________    Solid ion exchange of different small-pored zeolites with different metal     salts                                                                         or metal oxides                                                                               n Me, in,                                                                           n Cl.sup.-, out,                                                                    m Me/m Z                                          Example                                                                            Zeolite                                                                            Metal Salt                                                                          mole  mole  %     Figure                                      __________________________________________________________________________    4    Rho  PtCl.sub.2                                                                          2.6 · 10.sup.-5                                                            5.2 · 10.sup.-5                                                            1.0   3                                           5    ZK-5 RhCl.sub.3                                                                          4.9 · 10.sup.-5                                                            1.3 · 10.sup.-4                                                            0.9   4                                           6    Alpha                                                                              PdCl.sub.2                                                                          4.8 · 10.sup.-5                                                            9.6 · 10.sup.-5                                                            1.0   5                                           7    SAPO-42                                                                            PdCl.sub.2                                                                          4.8 · 10.sup.-5                                                            9.6 · 10.sup.-5                                                            1.0   6                                           8    SAPO-42                                                                            NiCl.sub.2                                                                          8.4 · 10.sup.-5                                                            1.6 · 10.sup.-4                                                            1.0   7                                           9    SAPO-42                                                                            NiO   8.5 · 10.sup.-5                                                            --    1.0   8                                           __________________________________________________________________________

It is clear that in all instances the solid state ion exchange takesplace practically completely and metal charges of approximately 1% byweight are achieved. The results of the conversion of thehexene-(1)/2,4,4-trimethylpentene-(1) mixture on the catalysts producedin accordance with the present invention are shown in FIGS. 3 to 8. Inall instances the hydrogenation of the hexene-1 is strongly preferred(i.e., the predominant portion of the introduced metal is located in thezeolite pores). In addition to the hydrogenation, an isomerization ofthe double bond on the metal takes place on the catalysts containingpalladium and nickel, at which time the n-hexene-(1) is converted to afar greater extent than the bulky 2,4,4-trimethylpentene-(1).

It is apparent from table 2 and FIG. 8 that the solid state ion exchangecan be carried out not only with metal halides but also with metaloxides. This makes it possible to carry out the solid ion exchange evenwithout the release of HCl gas, which can potentially be damaging forcertain zeolites.

Further variations and modifications of the foregoing will be apparentto those skilled in the art and such variations and modifications areattended to be encompassed by the claims that are appended hereto.

What is claimed:
 1. A modified molecular sieve produced by a methodcomprising mixing a calcined and activated zeolite with a sufficientamount of a metal compound to form a solids mixture, heating said solidsmixture in a current of inert gas to form a heated solids mixture,cooling said heated solids mixture and subsequently reducing said cooledsolids mixture in a current of hydrogen to produce small metal clustersfrom the cationically introduced metal; wherein said metal compound is anoble metal halide, a noble metal oxide, CuCl₂, or V₂ O₅ ; wherein saidzeolite is a small-pored zeolite selected from the group consisting ofzeolite ZSM-58, zeolite SAPO-42, zeolite Rho, and zeolite ZK-5; andwherein greater than 60% of the introduced metal is located in the poresand interstices of said small-pored zeolite.
 2. The modified molecularsieve according to claim 1, wherein said inert gas is helium ornitrogen.
 3. The modified molecular sieve according to claim 1, whereinsaid reducing is for 10 to 14 hours at 280° to 350° C.
 4. The modifiedmolecular sieve according to claim 3, wherein the flow rate of thehydrogen is about 15 cm³ /min.
 5. The modified molecular sieve accordingto claim 1, wherein said heating is at temperatures of 400° to 600° C.6. The modified molecular sieve according to claim 1, wherein saidcooling is to room temperature.
 7. The modified molecular sieveaccording to claim 1, said method further comprising rinsing withammonia.
 8. The modified molecular sieve according to claim 1, saidmethod further comprising as a pretreatment first preparing the Branstedacid form of the zeolite.
 9. The modified molecular sieve according toclaim 1, wherein >70% of the introduced metal is located in the poresand interstices of said small-pored zeolite.
 10. The modified molecularsieve according to claim 1, wherein said modified molecular sieve is ahydrogenation catalyst.
 11. The modified molecular sieve according toclaim 1, wherein said metal compound is PtCl₂, PdCl₂, or RhCl₂.
 12. Amodified molecular sieve produced by a method consisting essentially ofmixing a calcined and activated zeolite with a sufficient amount of ametal compound to form a solids mixture, heating said solids mixture ina current of inert gas to form a heated solids mixture, cooling saidheated solids mixture and subsequently reducing said cooled solidsmixture in a current of hydrogen to produce small metal clusters fromthe cationically introduced metal; wherein said metal compound is anoble metal halide, a noble metal oxide, CuCl₂, or V₂ O₅ ; wherein saidzeolite is a small-pored zeolite selected from the group consisting ofzeolite ZSM-58, zeolite SAPO-42, zeolite Rho, and zeolite ZK-5; andwherein greater than 60% of the introduced metal is located in the poresand interstices of said small-pored zeolite.
 13. The modified molecularsieve according to claim 12, wherein said metal compound is PtCl₂,PdCl₂, or RhCl₂.